Process for preparation of aldehyde and ketone organic peroxide compositions and the use thereof as polymerization initiators

ABSTRACT

Improved organic aldehyde and ketone peroxide compositions useful for initiating the polymerization of polyesters formed from the concurrent reaction of a beta dione such as 2,4pentanedione and a different (non-beta dione) ketone or aldehyde, for example methyl ethyl ketone, with aqueous hydrogen peroxide.

11 ite States Patent Leveskis Dec. 10, 1974 PROCESS FOR PREPARATION OF ALDEHYDE AND KETONE ORGANIC PEROXIDE COMPOSITIONS AND THE USE THEREOF AS POLYMERIZATION INITIATORS Inventor: Newton G. Leveskis, 49 Vallecito Ln., Walnut Creek, Calif. 91789 Filed: Feb. 5, 1973 Appl. N0.: 329,918

Related US. Application Data Division of Ser. No. 43,329, June 4, 1970, which is a continuation-in-part of Ser. No. 702,782, Feb. 5,

1968, which is a continuation-in-part of Ser. No. 473,855, July 21, 1965.

US. Cl. 260/861 Int. Cl. C081 21/00 Field of Search 260/861; 252/426, 329

[56] References Cited UNITED STATES PATENTS 3,349,040 10/1967 Kressin et a1. 252/182 3,377,407 4/1968 Kressin et al. 260/863 3,630,960 12/1971 Chetakian 252/426 Primary ExaminerHarold D. Anderson Assistant Examiner-E. A. Nielsen Attorney, Agent, or FirmTownsend and Townsend 5 7 ABSTRACT 26 Claims, 4 Drawing Figures PATENTEL; 1151: 1 01914 TEMP. c

TEMP.

IIO

3.853.967 SHEET F 2 A-MEK ALONE 13-20 T01 MEK TO 2,4 PENTANEDION 0-10 T01 D- 5 T01 n G- 5 T01 MEK TO 2,4 PENTANEDIONE WITH gms OF 70% t- BUTYL HYDROPEROXIDE IO 20 3O 4O 5O MINUTES 3 TO I MOLAR RATIO KETONE TO DIONE A-2,5 HEXANEDIONE MEK B-2,4 PENTANEDIONE MEK 1O 2O 3O 4O 5O 60 7O MINUTES PATENTEU E8 I 0 I974 'TEMP. c

TEMP. c

shear 2 or 2 5 T01 MOLAR RATIO KETONE TO 010m:

A-- 2,5 HEXANEDIONE MEK B-2,4 PENTANEDIONE MEK MINUTES FIG 3 QIOTOI MOLAR RATIO KETONE TO DIONE A2,5 HEXANEDIONE, MEK B -2,4 PENTANEDIONE, MEK

0 IO 20 3O 4O 5O 6O 70 MINUTES FIG 4 PROCESS FOR PREPARATION OF ALDEHYDE AND KETONE ORGANIC PEROXIDE COMPOSITIONS AND THE USE THEREOF AS POLYMERIZATION INITIATORS This is a division of copending patent application Ser. No. 43,329, filed June 4, 1970, which is a continuationin-part of patent application Ser. No. 702,782, filed Feb. 5, 1968, which in turn is a continuation-in-part of Ser. No. 473,855 filed July 21, 1965.

This invention relates to improved organic ketone and aldehyde peroxide compositions, to a method for their preparation, and to their use of polymerization initiators. In a preferred embodiment, a fire resistant organic ketone peroxide is provided that has advantages in catalyzing polyester resins.

The present invention departs from and improves upon earlier teachings through the use of a novel combination of peroxides formed concurrently from an aldehyde or ketone (other than a beta dione) such as methyl ethyl ketone and a beta dione such as 2,4- pentanedione. The beta dione and non-beta dione ketone or aldehyde are coreacted with hydrogen peroxide in conventional fashion to form a mixture of organic peroxides. The chemical structure of the end products found in the mixture is not known with certainty but is believed to be a variety of peroxide isomers and polymers in which both the methyl ethyl ketone or other ketone or aldehyde and 2,4-pentanedione or other dione collectively participate. The terms coreaction product and mixture are used herein to de scribe these new peroxides synthesized from the combination of the selected aldehyde or ketone and beta dione with hydrogen peroxide.

In the preferred embodiment, the new peroxide coreaction product is made in combination with water and a mutual solvent or dispersant in accordance with copending patent application Ser. No. 584,608, filed Oct. 5, 1966, now US. Letters Pat. No. 3,507,800, and is surprisingly stable and fire resistant. As a result, compositions containing about 35-60 percent of the organic perioxides by wieght can be prepared and the desired fire resistance still obtained. Thus, a composition has been prepared in large quantities containing 52 percent of the co-reaction of 2,4-pentanedione and methyl ethyl ketone that is so flame resistant that it has been approved by the Bureau of Explosives as being not subject to classification as an oxidizing materialunder Interstate Commerce Commission regulations.

Perhaps the most significant advantages of the new compositions (whether made with sufficient water to be fire resistant or not) relate to their utility as catalysts for polyester resins. Over a broad spectrum of the various polyester resins utilized commercially the new materials have proved superior on the average in the important characteristics desired in an organic peroxide catalyst. The new compositions when used with polyester resins exhibit faster gel times, higher peak temperatures, and shorter times to reach the peak temperature than has been possible with previously available catalyst systems of the same type. The present invention therefore provides compositions of broad utility that will satisfy the needs of the vast majority of catalyst users and will avoid the necessity of choosing a special catalyst depending upon the particular resin system being utilized. The present materials will give excellent results in almost all cases at room temperature and in most instances will be superior to all competitive peroxide catalysts. \Vithout intention of limiting the invention as claimed it is believed that the beta dione contributes the high peak temperatures while the other ketone or aldehyde contributes the fast gel times observed when using the new peroxide compositions.

The essential reactants for making the new compositions are hydrogen peroxide, a beta dione, and a different, i.e a non-beta dione or an aldehyde. Any different ketone or aldehyde is contemplated if it will coreact with the selected beta dione in the presence of hydrogen peroxide to form an organic peroxide co-reaction product so long as it is not a beta dione. Preferably, the selected aldehyde or different ketone, or mixture thereof, is free from aliphatic unsaturation. Otherwise, virtually any organic compound containing one or more aldehyde or ketone carbonyl groups may be selected with excellent results. Thus, both alkyl and aromatic groups may be present in the aldehydes and ketones used and these groups may contain any desired substituents such as halogen atoms, other alkyl or aryl groups, and diverse functional groups. Preferably, the selected aldehyde or ketone contains only carbon, hydrogen and oxygen atoms (from hydroxyl, acid, ester and ether linkages as well as the carbonyl group) and is limited to not more than about 20 carbon atoms for practical purposes. Representative examples of this broad area available for selection will appear hereinafter in the specific examples that have been prepared and studied.

The beta dione component may also be selected from a large number of possibilities so long as the requisite beta dione structure is present in the molecule. By beta dione structure is meant a structure in which two keto groups are separated by one carbon atom, as for example in the following structure:

in which the carbonyl carbon atoms are bonded to other than hydrogen. The beta dione selected contains not more than about 20 carbon atoms for practical purposes. Preferably, R and R of the beta dione are the same or different alkyl, cycloalkyl, or aryl groups which may contain non-interfering substituents such as the halogens. The rings may contain substituents such as alkyl groups if desired. Typical examples of beta diones are: 2,4-pentanedione, 2,4-hexanedione, 3,5- heptanedione, 7.9-octadecanedione, 5,7-decanedione- 2,4dimethyl, and the like. Typical beta diones containing cyclic groups are' l,3-butanedione-l-phenyl and l -cyclohexanone-2-acetyl.

In general, the end product is prepared by reacting the selected aldehyde or ketone such as methyl ethyl ketone and the beta dione such as 2,4-pentanedione with aqueous hydrogen peroxide in a hydrophilic fluid media. Conveniently, the reaction is executed in a mutual solvent or dispersant and the hydrogen peroxide is added as an aqueous solution. The conversion of the ketones to the organic peroxides is conventional with sufficient aqueoushydrogen peroxide being added to form at least appreciable organic peroxides therewith. A stoichiometric excess of hydrogen peroxide is generally used to insure completeness of the reaction. In general, the desired reaction is accelerated by heating the mixture to about 25-45C., preferably about 30-35 C. Depending upon the quantities, the preparative equipment and other factors, the reaction will be completed within a number of hours.

The reaction is suitably catalyzed by the addition of an acid catalyst such as sulfuric acid but the catalyst preferably takes the form of an acidic ion exchange resin. The catalyst-is suitably removed at the completion of the reaction. The reaction requires acidic conditions but this factor may be adequately met by the aqueous hydrogen peroxide which is acidic. The addition of acid or acidic ion exchange resin further promotes the reaction in most cases. An optimum product with respect to stability is obtained where the pH of the end reaction product is adjusted to about 4.0-5.5, preferably 4.5. Organic amines such as the heterocyclic amines-like pyridine have been found to be advantageous for adjusting the pH.

The amounts. of the various components of the final composition are subject to some variation. The water content should usually be at least about 18 percent in the final composition where fire resistance is sought but may be lower in some cases and may be as high as desired, consistent with practicality which demands a composition of sufficiently high peroxide content to render rapid catalysis of resin systems.

The proportion of the selected aldehyde or different ketone to beta dione is relatively critical. Best results are achieved where the selected aldehyde or different ketone is used in a ratio of 1 mole of beta dione to about 3-20 equivalent weights of the selected aldehyde or different ketone based upon the number of coreactive carbonyl sites therein. About 3-5 equivalent weights of the selected aldehyde or different ketone has given optimum results with the materials used to date.

Equivalent weight is used in the usual sense. For example, methyl ethyl ketone contains one coreactive carbonyl group and 3-5 moles should be used for each mole of beta dione. In the case of a polyfunctional nonbeta ketone such as 2,5-hexanedione having two coreactive carbonyl groups, only about 1.5-2.5 moles are needed for'each mole of beta dione.

In general, only aldehyde and ketone carbonyl groups are coreactive with the beta dione and hydrogen peroxide in the present invention. One exception to this rule has been found in the carbonyl group of a beta keto ester. in this special csse'the carbonyl group from the carbonyl group has been found to function as an aldehyde or ketone carbonyl group in addition to its ketone carbonyl group for coreaction with a beta dione and hydrogen perixode. Accordingly, acetoacetate esters are considered as having two coreactive carbonyl groups when determining the amount to be used in the present process. It should be understood that both carbonyl groups need not be reacted unless desired. 1f reaction of the keto carbonyl groups only is desired, the full molar quantity of about 3-5'moles of the acetoacetate ester is employed for each mole of 2,4- pentanedione and the ester is considered as having only one coreactive carbonyl group. Similarly, all carbonyl groups of other non-beta aldehydes and ketones need not be reacted by appropriately limiting the proportions of reactants. s

in the preferred fire resistant compositions, sufficient mutual solvent or dispersant is added to the composition to achieve a homogeneous or non-separating composition. This will depend upon the proportion of the other ingredients and the type of materials used. in

most cases the solvent or dipsersant will constitute the balance of the composition in addition to the water and organic peroxides. Preferred proportions for the composition are about 18-20 percent water, about 30 percent solvent or dispersant and about 50-52 percent peroxides. In these ranges a composition having an active oxygen content of about 10-1 1 percent can be obtained.

The mutual solvents or dispersants include those described in said US. Letters Pat. No. 3,507,800. In general, a preferred group of materials can be classified as water soluble aliphatic, preferably hydrocarbon, polyoxy alkanes and esters, although any mutual solvent or dispersant capable of forming a homogeneous composition with the water and the organic peroxide and which does not react therewith to destroy the peroxide-water nature of the composition may be used. It appears that the crucial aspect of the useable materials for purposes of homogenation is the presence of a plurality of oxygen atoms. Thus, polyalkylene glycols, such as polyethylene glycol, polypropylene glycol and other aliphatic polyhydroxy compounds which are liquid or soluble in water and which will dissolve or disperse both the peroxide and water or render them mutually miscible, are contemplated within the scope of the present invention. Other suitable polyoxy solvents and dispersants include water soluble polyethers, polyepoxies, polyaldehydes and polyketones since they all contain the requisite oxygen and are aliphatic in nature, provided of course that they are a mutual solvent or dispersant for the peroxide in water and are inert thereto.

As noted, the mutual solvent or dispersant may be a polyoxy alkane or a polyoxy ester. The ester group provides the requisite plural oxygen atoms and may be present alone or in addition to the other types of polyoxy linkages noted above. Thus, suitable solvents or dispersants include esters such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, methoxy triglycol acetate, polypropylene carbonate, trimethyl phosphate, silicate esters and the like.

The following example will illustrate the general method of preparation of the new compositions:

EXAMPLE I in a suitable glass round bottom flask, fitted with agitator, reflux condenser and thermometer were charged:

30 g. Polypropylene Glycol 425 24 g. Methyl Ethyl Ketone 6 g. 2,4-Pentanedione 9 g. Dowex 50 WX-S The mixture was cooled to C. and 40 g. of 50% w H 0 was added over a period of 45-50 minutes, The temperature was maintained at 30-35 C. and the reaction continued for 16 hours. Upon completion of the reaction, the catalyst was removed by filtration and the pH of the resultant liquid peroxide formulation adjusted to 4.0 to 5.5, preferably 4.5 using pyridine and measuring apparent pH on 'a Leeds & Northrup pH meter. The resultant peroxide was then treated to remove excess water and consentrate the peroxide to an active oxygen content of 10.50 to 10.55 percent. The composition was about 18% H 0 30% Polypropylene Glycol 425 A large scale pilot plant run was conducted in the following manner:

EXAMPLE ll Into a 30 gallon glass lined pfaudler reactor, equipped with agitator, temperature probe and fume exhaust were charged:

40 lbs. oz. Polypropylene Glycol 425 8 lbs. 1 oz. 2,4-Pentanedione 32 lbs. 4 oz. Methyl Ethyl Ketone 12 lbs. Dowex 50WX-8 The materials were mixed and, by use of a brine bath circulated through the jacket of the reactor, cooled to 15 C. Then 58 lbs. s 8 oz. of 50%w H 0 were charged over a period of 1.25 hours, maintaining the temperature at 3335 C. by jacket cooling. The reaction was continued for 21 hours, maintaining the temperature. Upon completion of the reaction, the reactants were filtered to remove catalyst. The peroxide solution of about 18 gallons in volume was adjusted to pH 4.5 with 105 ml. of reagent grade pyridine. The partially dried finished product had the following composition:

Active Ox gen: 10.50% Pol ropy ene Glycol 425: 30.00% Aliphatic Hydrocarbon Ketone Peroxrdes: 52.00% Water: 18.00%

A sample of the material of Example 11 was forwarded to the Bureau of Explosives for testing. The Bureau of Explosives determined the flash point of the material to be above 100 F. and to not detonate under blasting cap initiation. The Bureau also determined that the sample did not become ignited readily-by external flame. when a porous wick was placed in a portion of the sample and ignited, the sample (which is a clear transparent water-white liquid) burned fairly steadily without noticeable acceleration until nearly exhausted when some flaming occurs. The Bureau of Explosives held the sample to not be subject to classification as an oxidizing material under Interstate Commerce Commission regulations.

To demonstrate the advantageous performance of the new compositions in catalyzing polyester resin systerns, a series of experiments were performed. For comparison, a standard commercial grade of methyl ethyl ketone peroxide (MEKP) was employed together with a fire resistant methyl ethyl ketone peroxide (FR- MEKP) prepared in accordance with the teachings of the previously referenced US. Pat. No. 3,507,800. The material prepared in Example 11 was used as representative of the present invention.

The following Table lists catalyst performance with a series of commercially available polyester resins together with the promoters used where applicable and the amount of catalyst employed. The bath temperature is the temperature of the medium surrounding the vessel in which the polymerization reaction was executed. The Table shows the resin temperature at the commencement of the reaction, the peak temperature of the reaction, and the time to reach the peak temperature. As is well understood, a high peak temperature, especially where the reaction is run in a low temperature environment, and a short time to reach the peak temperature are the desired attributes of a good catalyst.

TABLE 1 Resin: Hetron 92 Promoter 0.5%w Cobalt Naphthenate 6% Catalyst 1.0%w

A. Bath Temperature 9.0 C.

Catalyst MEKP FR-MEKP EXAMPLE l1 Resin Temperature 100C 100C 100C Peak Temperature 132.3C 130 "C 136.8C.

Peak Time: 00 43'00" 26'00 B. Bath Temperature 250C Catalyst MEKP FRMEKP EXAMPLE l1 Resin Temperature 25.0C. 25.0C. 25.0C. Peak Temperature 157.0C. 154.0C 157.8C. Peak Time 15'00" 15'0 1100" Resin: Plaskon PE 258 Catalyst 1.0%

A. Bath Temperature C.

v Catalyst MEKP FR-MEKP EXAMPLE [1 Resin Temp, C. 10.0 10.0 10.0 Peak Temp., C. 1380 124.8 138.0 Peak Time 124'00" '00 8100" B. Bath Temperature 90C.

Catalyst MEKP FR-MEKP EXAMPLE ll Resin Temp. C. 10.0 10.0 10.0

Peak Temp. C. 143.0 140.0 142.0

Peak Time 00" 79'00" 68'00" C. Bath Temperature C.

Catalyst MEKP FR-MEKP EXAMPLE 11 Resin Temp.. C. 14.5 14.5 14.5 Peak Temp.. C. 147.4 133.8 147.0 Peak Time 7700" 61 '00" 52'00" D. Bath Temperature 210C.

Catalyst MEKP FR-MEKP EXAMPLE l1 Resin Temp., C. 23.0 23.0 23.0

Peak Temp., C. 166.2 163.3 163.0

Peak Time 34'00" 32'00" 24'00" Resin: Sherwin-Williams US9UA61 Peak Time Catalyst 1.0%w A. Bath Temperature 50C.

Catalyst MEKP FR-MEKP EXAMPLE ll Resin Temp. C. 8.2 8.3 8.7 Peak Temp, C. 10.3 12.5 46.2 Peak T me Over 5 hrs Over 5 hrs 2 hrs 45 mins 8. Bath Temperature 110C. I

Catalyst MEKP FR-MEKP EXAMPLE I! Resin Temp C. 14.8 14.8 14.8 Peak Temp, C. 15.2 l8.0 144.8 Peak Time Over 2 hrs Over 2 hrs 70'00" C. Bath Temperature 13.0C.

Catalyst MEkP FR-MEKP EXAMPLE I: Resin Temp, C. 19.0. 19.0 19.0 Peak Temp, C. 152.9 l37.5' l58.0 Peak Time 11 1'00" 8600'1 43 '00" D. Bath Temperature 210C.

Catalyst MEKP FR- EXAMPLE ii MEKP Resin Temp. C. 24.0 24.0 24.0 Peak Temp, C. 163.0 167.8 171.3 62Iml' 45lml! 26Imll The following example illustrates the necessity for forming a co-reaction peroxide product of the selected aldehyde or different ketone' such as methyl ethyl ketone and the beta dionesuch as 2.4-pentanedione. Thus, when 2,4-pentanedione is added to preformed methyl ethyl ketone peroxide. the catalyst performance is substantially inferior to a catalyst prepared in accordance with the present invention. in this experiment, four samples of ketone peroxides were prepared and are identified as follows:

with Example I1 (52% active peroxide).

B. A commercial methyl ethyl ketone peroxide (60% active peroxide).

C. -A commercial methyl ethyl ketone peroxide to I which has been added 1% by weight of 2,4-

30 pentanedione (59% active peroxide).

D. A commercial methyl ethyl ketone peroxide to which has been added 5% by weight of 2,4- pentanedione (55% active peroxide).

The above four catalysts were then used for curing 35 the referenced polyester resins. All materials were used on an equal weight basis. The figures given for gel time represent the time until a gel structure was formed from the starting polyester resin. The other notations are used as before.

TABLE u Rcsinz" Polylite 8224A Temperature 25.0 0. Catalyst 0.5%

' Catalyst A B D Gel Time 7'30" 33'30" 39'45" 45'20" Peak Time I6'OO" 47'00" 53'00" 58'00" Peak Temp. C. l55.0 153.0 152.8 I561) Resin: ADM 753 IMTI6 v Temperature 250C. Catalyst il.5%w

Catalyst A B C D oer Time [8'00" z'i'oo" 26'00" 2100" Peak Time 38'30 57'00" 52'00", 38'00" Peak Tcmp..' C. 7 143.0 I 135.0 136.5- 7 145.0 Resin: (0 ilezyn 277W I I H Temperature 25.(l(.. I Catalyst =05Kw I Catalyst A a C 0 Gel Time 19'00" 25'00' 28 '00" 36'00" Peak Time 40'00" 48'00" 52'00 57'()()" Peak Temp. "C. ll2.0 132.0 I335 i371) Resin: lletron 92 I v I Temperature 250C. Catalyst O.5kw

Promoter 0.5%w Cobalt Naphthen'ate 671 7 Catalyst A B c o 7 col Time "7'00" 1515" 1500" 10/00" Peak Time 1700" 2800" 2700" 23'30" Peak Temp. C. 154.0 149.0 152.0 157.0

The following experiments illustrate the advantageous properties of the present compositions as influenced by a variation in the ratio of the selected aldehyde or different ketone such as methyl ethyl ketone to cess used is essentially that of Example I except that the quantities of the materials used here are half that of Example I. Also, in this Example, the mixture was stirred in a flask in a water bath set at 44 C. for a period of beta dione such as 2,4-pentanedione in the preparation 3 hours. The end product was adjusted to a pH of 5 of them. The work demonstrates the significant advanwith pyridine. tage of a composition in which the aldehyde or differ- TABLE m ent ketone (methyl ethyl ketone) is used in a proportron relative to the beta dione (2,4-pentaned1one) m Molar Ratio Methyl the preparation of the organic peroxide composition or Eth Ketone to close to the preferred ratio of about 3-5:l. emanedlone A. grm Polypro ylene Glycol EXAMPLE IV gms x62]; 1 Eth l Ketone Three fire resistant compositions were prepared in g on Exchange Resin accordance with the method and techniques of Exam- 15 (Dowex 5 wX g) B. 15 gms Pol ropylene Gl col ple II but util z ng the proportion of materials listed 1 gm 24 Pg'glanedime y :1 low. Composition A contains a 4.1 weight ratio (5.5.1 14 gms Mam 15th Ketone molar ratio) of methyl ethyl ketone to 2,4- 2 O gms 550M 8 pentanedione with compositions B and B being vana- C 5 Gycol tions thereof. 20 L8 gms Zlgentanedione 10:1

[3.2 gms Methyl Ethyl Ketone 20 gms HOOH 50% 4.5 gms Dowex 50WX-8 D. 15 gms Polypropylene Glycol A. 30.0 g. Polypropylene Glycol 425 (5.5:] molar mm) 3.2 gms 2,4-pentanedione 5:1

6.0 g. 2.4-Pentanedione ll.8 gms Methyl Ethyl Ketone 24.0 g. Methyl Eth l Ketone 20 gms HOOH 50% 9.0 g. Dowex 50 8 4.5 gms Dowex 50WX:8 43.5 g. H202 50%w E. 15 gns Polypropylene Glycol 4.7 gms 2,4-pentanedione 3:] B. 10% Increase of Difunctional Ketone (5.05:l 10.3 gms Methyl Ethyl Ketone molar ratio) 20 gms HOOI-I 50% 4.5 gms Dowex 50WX-8 30.0 g. Polysropylene Glycol 425 F. 15 gms Polypropylene Glycol 6.6 g. 2.4 entanedione 6.1 gms 2,4- ntanedione 2:l 24.0 g. Methyl Eth l Ketone 8.9 gms Me yl Ethyl Ketone 9.0 g. Dowex 50 X8 20 gms HOOI-I 50% 44.82g. H202 50%w 4.5 gms Dowex 50WX-8 G. 15 gms Polypropylene Glycol C. 10% increase of Monofunctlonal Ketone (6.l:l 3 2 gms 2,4 ranedi 5;|

molar ratio) 11.8 gms Methyl Ethyl Ketone 20 gms Tert Butyl Hydroperoxide 30.0 g. Pol ropylene Glycol 425 g Dow x WX-8 6.0 g. 24 entanedione 28.4 g. ltD'lgthyl githyl Ketone .0 wex 0WX8 46.862. H20; 50%; The above compositions were then checked for gel 40 time and time-temperature performance with the polyester resin known as Hetron 92. 35 grams of Hetron The above three materials were treated as in Examresin was combined with 0.5%wt. of each of the peroxple I. The finished products were then compared in a ide compositions of Table III together with 0.5%wt. of polyester resin system with the following results. Aconcobalt octanoate (6%). The initiated resin in a 1 oz. ventional methyl ethyl ketone peroxide was employed 45 container was maintained in a water bath at a temperafor comparative purposes. All materials are used on an ture of 24 C. Temperatures of the resin were taken equal weight basis. every few minutes and the results plotted on a curve.

Resin: Plaskon PE 258 Temperature 2l .0C. Catalyst A B C MEILP Gel Time 13'15" 13'45" 1400" 15'45" Peak Time 27'00" 27l4" 27'45' 32'00" Peak Temp, C. l66.8 l7 5.8 I628 I675 The following Example again shows the criticality of The results are shown in FIG. 1 of the accompanying the ratio of the selected aldehyde or different ketone to drawings. The curve labeled A utilized composition A beta dione together with the unexpected advantages of Table III. The letters on the other curves correspond obtained by using the 3-5:l ratio of the preferred emto formulations having the same letter in Table III. bodiment. In addition, the Example illustrates the criti- As will be seen from FIG. 1, curve A with its relacality of executing the co-reaction with hydrogen pertively low peak temperature resulted from the use of xide as disting ished from organic peroxides such as MEK peroxide that does not have the benefit of the cot-butyl hydroperoxide. reaction process of this invention. Curves B through E EXAMPLE V A series of peroxide co-reaction products were made from the materials shown in Table III below. The prorepresent performance curves of compositions prepared in accordance with this invention. The proportions of co-reactants of D and E, i.e., 35:1 represent the preferred embodiment. Curve F contains too little methyl ethyl ketone co-reactant and is outside the scope of this invention. While such a composition offers a high peak temperature, the shifting of the curve to the right, which indicates an increase in reaction time, is unacceptable because of the increased time. Curve G results from the use of an organic peroxide (tbutyl hydroperoxide) instead of hydrogen peroxide as required by the present invention. Such a composition is not suitable for the room temperature curing of polyesters and essentially fails to effect any cure at all. Hydrogen peroxide must be used in the present invention and organic peroxides cannot be substituted for it.

The following Examples illustrate the broad applicability of the invention to aldehydes and ketones in addition to the methyl ethyl ketone used in the preceding experimental work. Also illustrated is the use of other types of solvents and diluents in which to execute the preparative reaction and for storing and using the reaction product in combination therewith. By way of summary. the following types of aldehydes and ketones were prepared.

' TABLE IV Categories of Starting Materials For Co-reaction With Hydrogen Peroxide l. Aliphatic Aldehyde and 2,4-Pentanedione 2. Aromatic Aldehyde and 2,4-Pentanedione 3. Methyl Ethyl Ketone and 2,4-Pentanedione prepared in an ester-type diluent 4. Keto-ester (other than beta keto ester) and 2,4-

Pentanedione 5. Difunctional Ketone and 2,4-Pentanedione 6. Alkyl-aryl Ketone and 2,4-Pentanedione in an ester-type diluent 7. Beta keto ester and 2,4-Pentanedione 8. Alkyl Branched chained alkyl ketone and 2,4-

Pentanedione 9. l-lydr'oxy substituted alkyl ketone and 2,4- Pentanedione l0. Methyl ethyl ketone in methyl carbitol solven and 2,4-Pentanedione 11. Additional aliphatic Pentanedione 12. Additional aliphatic ketone and 2,4-

Pentanedione l3. Cyclic aliphatic ketone and 2,4'-Pentanedione Specific compositions illustrating each of the Table I categories were prepared in accordance with the procedure described in Example I using the materials listed in the following Example. The approximate composition of the end reaction product is also indicated.

ketone and 2,4-

- l2 EXAMPLE Vl-Continued Mole Patio Weight Reactants Grams Approximate Composition Ketone Peroxides Methyl Carbitol 25% 20 5% 3. Dimethyl Phthalate Methyl Ethyl Ketonc 2,4s-gentanedione Maori-50% excess Approximate Composition Ketone Peroxides Dimethyi Phthalate 38% H20 2% excess Approximate Composition Kctorie Peroxides Methyl Carbitol H, O

5. Meth lCarbitol 2,5- xanedione 2.4-Pentanedione Dowex 50WX-l2 HUGH-50% Approximate Composition Ketone Peroxides 44% Methyl Carbitol H2O l 7% 6. Dirnethyl Phthalate Acetophenone 2,4-Pentanedione H Hedi-50% 5 Ix) arowoq excess Approximate Composition Ketone Peroxides Dimethyl Phthalate Benzophenone can be substituted for the acetophenone in this example with equivalent results.

7. Methyl Carbitol Methyl Acetoacetate 2,4Pentanedione Dowex SOWX-l2 Pinch-50% G ow LII

EXCESS Approximate Composition Ketone Peroxides Methyl Carbitol 8. Methyl Carbitol Methyl lsobutyl Ketone 2,4Pentanedione Dowex 5OWX-l2 HOOH-50% 7 L535 OLII excess Approximate Composition Ketone Peroxides Methyl Carbitol H ,0

9. Methyl Carbitol Diacetone Alcohol 2,4-Pentanedione Dowex 50WX-l2 HOOH-50% S P-r 5 om LIILII excess Approximate Composition Ketone Peroxide Methyl Carbitol Methyl C arbitol Methyl Ethyl Ketom: 2.4-Pentnnedionc Dowex SOWXJZ HOOH-Sll'k- EXCCSS EXAMPLE V1Continued Mole Weight Grams Patio Reaetants A roximate Composition K thne Peroxides 50% Methyl Carbitol 34% H 16% Methyl Carbitol Methyl Prop 1 Ketone 2.4-Pentane ione Dowex 50WX-l2 HOOH-50% excess Approximate Composition Ketone Peroxides Methyl Carbitol Methyl Carbitol Acetone 2,4-Pentanedione Dowex 50WX-12 HOOH-50% excess Approximate Composition Ketone Peroxides 45% Methyl Carbitol Methyl Carbitol Cyclohexanone 2.4-Pentanedione Dowex 50WX-12 HO0H-50% W out Approximate Composition Ketone Peroxides Methyl Carbitol of the catalysts of Example VI was used to initiate the polymerization of .Plaskon PE 258 and was added thereto in a 1 percent by weight concentration. Bath temperatures are indicated.

The following Table shows the observed results. For comparison a standard methyl ethyl ketone peroxide The following example illustrates the applicability of the invention to beta diones' in addition to the 2,4 pentanedione used in the preceding experimental work. The additional beta diones used are typical of the results obtainable with all of the others within the generic scope previously defined.

EXAMPLE vn Two compositions were prepared in accordance with the procedure described in Example I using the materials tabulated below. The approximate composition of the end reaction product is also indicated.

These catalysts exhibit the same advantageous properties noted with respect to the compositions containing 2,4-pentanedione in the preceding Examples. As typical of their performance, catalyst compositions l4 and 15 were used to initiate the polymerization of Plaskon PE 258 in a 1 percent by weight concentration at a bath temperature of 20 C. The following results were observed. For comparison a standard methyl ethyl ketone peroxide (MEKP) and catalyst composition number 10 of Example V1 were used under the same conditions with the same resin.

Catal St MEKP l0 l4 l5 (MEKP) was used to polymerize the same resin system y and its performances is also shown. Catalyst numbers g i gemp jgg8 2 21;

- ea emp.. refer to the same number sequence used in Example peak Time TABLE V Bath Temperature 21 C. I Catalyst number MEKP 1. 2. 3. 4. 5. 6.

Resin temperature, C. 21 21 21 21 21 21 21 Peak temperature, C. 169 164.3 160.1 173 156 173.1 169.7 Peak time 35'30" 24'30" 30'00" 30'30" 29'30" 30'30" 33'00" Bath Temperature 21.5 C.

Catalyst number MEKP 7. 8. Resin temperature. C. 21.5 21.5 21.5 Peak temperature, C. 166 172 166 Peak time 31'00" 18'30" 29'00" Bath Temperature 23 C.

Catalyst number MEKP 9. 10. ll. Resin temperature. C. 23.0. 23.0 23.0 23.0 Peak temperature. C. 166 169 164 Peak time 37'30" 35'00" 33'00" 33'30" Bath Temperature 21 C.

Catalyst number MEKP l2. l3. Resin temperature. C. 21.0 21.0 21.0 Peak temperature, C. 168 164 174 Peak time 31'30" 29'30" 20'30" The following Example illustrates the of co-reacting a beta dione with the selected other carbonyl compound-in order to achieve the desired results.

- which 0.5 percent wt. of cobalt octanoate (6%) was added. Polymerization conditions were maintained at 22-23-C. The reactions were monitored and the results plotted as may be seen in FIGS. 2, 3 and 4 of the drawings. The materials used in making the peroxide compositions are shown in Table VI.

TABLE VI Mole Ratio 3:5 Ziilexinedione gms Methyl Ethyl Ketone grrs HOOl-l 50% grrs Dowex 50WX-8 grns Polypropylene Glycol 425 grm 2,4-Pentanedione .3 gns Methyl Ethyl Ketone HOOH 50%- grns Dowex 5,0WX-8.

amourut oow JAN- All of the compositions of Table VI designated as A contain a dione that is not a beta dione. All samples marked B contain the beta dione required by the pres-' ent invention. Comparisons have been made at various ratios of the selected carbonyl compound (methyl ethyl ketone) relative to the dione. As may be seen from FIGS. 2-4, in all cases the compositions made with the requisite beta dione are vastly superior in performance as compared with the compositions which do not con- I tain' the beta dione. I

Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is understood that certain changes and modifications may be pracpolyester and vinyl monomer to free radical polymerization conditions in the presence of a polymerization initiating amount of an organic peroxide composition, the improvement comprising using as said organic peroxide composition a composition prepared by concurrently reacting a beta dione of up to about 20 carbon atoms of the structure:

in which R and R are individually selected from the group consisting of alkyl, cycloalkyl, and aryl with a different carbonyl compound selected from the group consisting of ketones and aldehydes of up to about 20 carbon atoms free from aliphatic unsaturation and containing only carbon, hydrogen, and oxygen in a ratio of 1 mole of beta dione to about 3-20 equivalent weights of different carbonyl compound based upon the number of co-reactive carbonyl groups therein in anacidic hydrophilic fluid medium containing sufficient aqueous hydrogen peroxide to form appreciable amounts of organic peroxides therewith. I

2. A process in accordance with claim 1 wherein the is 1 mole of beta dione'to about 3-5 equivalent weights of said different'carbonyl compound.

. 3. A process in accordance withclaim 1 wherein an acidic ion exchange resin is added to said fluid medium and is separated therefrom at the conclusion of thereaction.

4. A process in accordance with claim 1 and includlug-the step of adjusting the pH of the reaction product to about 4.0-5.5.

5. A process in accordance with claim 1 and including the step of heating the reaction mixture to about 25-45 C. to'promote said'concurrent reaction.

6. A process in accordance with claim 1 wherein the reaction mixture contains sufficient water to impart fire resistance to the fluid medium containing the reaction product.

7. A process in accordance with claim 2 wherein said different carbonyl compound contains an aromatic 8. A process in accordance with claim 2 wherein said different carbonyl compound is aliphatic.

9. A processin accordance with claim 2 wherein said different carbonyl compound contains more than one carbonyl group for co-reaction so that its equivalent weight in said process is less than its molecular weight.

10. A process in accordane with claim 2 wherein said different carbonyl compound isa ketone.

11. A process in accordance with claim 2 whereinsaid different carbonyl compound is an aldehyde.

ticed within the spirit of the inventionas limited only 1 by the scope of the appended claims.

What is claimed is: I

1. In the method for cross linking an essentially linear unsaturated polyester of a polycarboxylic acid anda P W h a vinyl m me isinssubi s ns said 12. A process in accordance with claim 2 wherein said different carbonyl compound is methyl ethyl ke tone.

13. A process in accordance with claim 2 wherein said different carbonyl compound is methyl acetoacsaid different carbonyl compound is diacetone alcohol.

16. A process in accordance with claim 2 wherein said different carbonyl compound is methyl propyl ketone.

17. A process in accordance with claim 2 wherein said difi'erent carbonyl compound is acetone.

18. A process in accordance with claim 2 wherein said different carbonyl compound is cyclohexanone.

19. A process in accordance with claim 2 wherein said different carbonyl compound is 2-ethyl hexanal.

20. A process in accordance with claim 2 wherein said different carbonyl compound is benzaldehyde.

21. A process in accordance with claim 2 wherein said different carbonyl compound is ethyl levulinate.

22. A process in accordance with claim 2 wherein 

1. IN THE METHOD FOR CROSS LINKING AN ESSENTIALLY LINEAR UNSATURATED POLYESTER OF A POLYCARBOXYLIC ACID AND A POLYOL WITH A VINYL MONOMER COMPRISING SUBJECTING SAID POLYESTER AND VINYL MONOMER TO FREE RADICAL POLYMERIZATION CONDITIONS IN THE PRESENCE OF A POLYMERIZATION INITIATING AMOUNT OF AN ORGANIC PEROXIDE COMPISITION, THE IMPROVEMENT COMPRISING USING AS SAID ORFANIC PEROXIDE COMPOSITION A COMPOSITION PREPARED BY CONCURRENTLY REACTING REACTING A BETA DIONE OF UP TO ABOUT 20 CAR BON ATOMS OF THE STRUCTURE:
 2. A process in accordance with claim 1 wherein the ratio of beta dione to said different carbonyl compound is 1 mole of beta dione to about 3-5 equivalent weights of said different carbonyl compound.
 3. A process in accordance with claim 1 wherein an acidic ion exchange resin is added to said fluid medium and is separated therefrom at the conclusion of the reaction.
 4. A process in accordance with claim 1 and including the step of adjusting the pH of the reaction product to about 4.0-5.5.
 5. A process in accordance with claim 1 and including the step of heating the reaction mixture to about 25*-45* C. to promote said concurrent reaction.
 6. A process in accordance with claim 1 wherein the reaction mixture contains sufficient water to impart fire resistance to the fluid medium containing the reaction product.
 7. A process in accordance with claim 2 wherein said different carbonyl compound contains an aromatic group.
 8. A process in accordance with claim 2 wherein said different carbonyl compound is aliphatic.
 9. A process in accordance with claim 2 wherein said different carbonyl compound contains more than one carbonyl group for co-reaction so that its equivalent weight in said process is less than its molecular weight.
 10. A process in accordane with claim 2 wherein said different carbonyl compound is a ketone.
 11. A process in accordance with claim 2 wherein said different carbonyl compound is an aldehyde.
 12. A process in accordance with claim 2 wherein said different carbonyl compound is methyl ethyl ketone.
 13. A process in accordance with claim 2 wherein said different carbonyl compound is methyl acetoacetate.
 14. A process in accordance with claim 2 wherein said different carbonyl compound is methyl isobutyl ketone.
 15. A process in accordance with claim 2 wherein said different carbonyl compound is diacetone alcohol.
 16. A process in accordance with claim 2 wherein said different carbonyl compound is methyl propyl ketone.
 17. A process in accordance with claim 2 wherein said different carbonyl compound is acetone.
 18. A process in accordance with claim 2 wherein said different carbonyl compound is cyclohexanone.
 19. A process in accordance with claim 2 wherein said different carbonyl compound is 2-ethyl hexanal.
 20. A process in accordance with claim 2 wherein said different carbonyl compound is benzaldehyde.
 21. A process in accordance with claim 2 wherein said different carbonyl compound is ethyl levulinate.
 22. A process in accordance with claim 2 wherein said different carbonyl compound is 2,5-hExanedione.
 23. A process in accordance with claim 2 wherein said different carbonyl compound is acetophenone.
 24. A process in accordance with claim 2 wherein R1 and R2 are alkyl groups.
 25. A process in accordance with claim 2 wherein said beta dione is selected from the group consisting of 2,4-pentanedione, 2,4-hexanedione, and 3,5-heptanedione.
 26. A process in accordance with claim 2 wherein said beta dione is 2,4-pentanedione and said different carbonyl compound is methyl ethyl ketone. 